Smolentsev G, Guilera G, Tromp M, Pascarelli S, Soldatov A V
Center for Nanoscale Structure of Matter and Faculty of Physics, Southern Federal University, Rostov-on-Don 344090, Russia.
J Chem Phys. 2009 May 7;130(17):174508. doi: 10.1063/1.3125940.
A method for the analysis of time-resolved x-ray absorption near edge structure (XANES) spectra is proposed. It combines principal component analysis of the series of experimental spectra, multidimensional interpolation of theoretical XANES as a function of structural parameters, and ab initio XANES calculations. It allows to determine the values of structural parameters for intermediates of chemical reactions and the concentrations of different states as a function of time. This approach is tested using numerically generated data and its possibilities and limitations are discussed. The application of this method to a reaction with methylrhenium trioxide catalyst in solution, for which experimental data were measured using stopped-flow energy-dispersive x-ray absorption spectroscopy technique, is demonstrated. Possibilities and limitations of this experimental technique are also discussed.
提出了一种分析时间分辨X射线吸收近边结构（XANES）光谱的方法。该方法结合了一系列实验光谱的主成分分析、作为结构参数函数的理论XANES的多维插值以及从头算XANES计算。它能够确定化学反应中间体的结构参数值以及不同状态的浓度随时间的变化。使用数值生成的数据对该方法进行了测试，并讨论了其可能性和局限性。展示了该方法在溶液中用三氧化甲基铼催化剂进行的反应中的应用，该反应的实验数据是使用停流能量色散X射线吸收光谱技术测量的。还讨论了这种实验技术的可能性和局限性。
